Identification of volatile compounds from fruits aroma and citrus essential oils and their effect on oviposition of Ceratitis capitata (Diptera: Tephritidae).

Ceratitis capitata (Wiedemann), also known as the Mediterranean fruit fly, is one of the most serious pests for several fresh fruit commodities causing extensive fruit losses worldwide. The response of C. capitata adults to fruit and nonfruit volatiles has been extensively studied. However, the linkage between fruit volatiles and the female ovipositional choice has not been fully elucidated. The present study focused on identifying the volatile organic compounds emitted by detached intact fresh fruits (oranges, lemons, bergamots, and apples) and citrus essential oils and evaluate their effect on Mediterranean fruit fly oviposition. There were more than 130 and 45 volatiles compounds detected in fruits odors and citrus essential oils, respectively. The volatile profile of fruits was dominated either from terpenes and terpenoids or from esters of butanoic, hexanoic, and octanoic acids while limonene was by far the most abundant compound in all citrus essential oils. Oviposition of C. capitata was strongly affected by volatiles emanated from both intact fruit and the citrus essential oils. Regarding the volatiles of the intact fruits, the odor of sweet orange elicited strong oviposition responses to females, while bergamot had the least stimulatory effect on oviposition. Bergamot oil also elicited the least oviposition stimulation compared to sweet orange and lemon essential oils. Our discussion elaborates on the role of fruit volatiles on host finding behavior and fruit susceptibility to C. capitata infestation and includes possible practical implication of the above findings.

Targeted Multiresidue Method for the Analysis of Different Classes of Pesticides in Agro-Food Industrial Sludge by Liquid Chromatography Tandem Mass Spectrometry.

Sludge generated after washing of fruits and vegetables during agro-food processes is a complex matrix and selective methods for the identification and quantification of pesticides' residues are necessary in order to achieve a sustainable and effective management of the total sewage. The present work describes the development and validation of a reliable, simple and fast analytical method based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) for the determination of 47 pesticides of different chemical classes, including organosphosphates, pyrethroids, neonicotinoids, triazoles and others, in sludge samples after QuEChERS sample preparation. The necessity of the individual steps of QuEChERS was investigated and the LC-ESI-MS/MS conditions were optimized to achieve maximum sensitivity of the target analytes. The method limits of detection (LODs) ranged between 0.0005 mg/kg (imidacloprid) and 0.05 mg/kg (beta cyfluthrin). The recoveries ranged between 71-120% and the repeatability of the method was ≤25% expressed as relative standard deviation. The method was applied to sludge samples generated after washing of fruits in an agro-fruit-packaging unit in Greece. The results showed the presence of 37 pesticides' active substances with concentrations ranging from low ppbs, such as fludioxinil (5 µg/kg) up to low ppms such as beta cyfluthrin (3.5 mg/kg) and with their sum concentration reaching up to 19 mg/kg.

Determination of azoxystrobin, topramezone, acetamiprid, fluometuron and folpet in their commercially available pesticide formulations by liquid chromatography.

A rapid, simple, precise and accurate high performance liquid chromatographic (HPLC) analytical method was developed and validated for the determination of the active substances (a.s.) azoxystrobin, topramezone, acetamiprid, fluometuron and folpet in their respective commercially available formulations. The method was used for the analysis of samples under the frame of the national quality control program of plant protection products in the Greek market. Chromatographic separation of the active substances from additives and co-formulants is achieved using isocratic elution with acetonitrile and 0.1% phosphoric acid solution (60:40 v/v) at a flow rate of 0.4 mL min-1 on a C18 monolithic column (Chromolith Performance-RP18e 100 × 4.6 mm) and UV detection at 230 nm. Validation parameters of the method fulfilled acceptability criteria. Recovery of all individual compounds was in the range 97.8-100.9%. Precision expressed as relative standard deviation was lower than the theoretical values of the modified Horwitz equation. Correlation coefficients of linearity of response were better than 0.999. The benefits of the proposed method are significant reduction in analysis time and total cost since all analytes were determined with the same extraction procedures and chromatographic system. Analysis of real samples for all active ingredients confirmed fitness for purpose of the suggested method.

Reynoutria sachalinensis extract elicits SA-dependent defense responses in courgette genotypes against powdery mildew caused by Podosphaera xanthii.

Powdery mildew (PM) caused by Podosphaera xanthii is one of the most important courgette diseases with high yield losses and is currently controlled by fungicides and sulphur applications in conventional and organic production. Plant derived elicitors/inducers of resistance are natural compounds that induce resistance to pathogen attack and promote a faster and/or more robust activation of plant defense responses. Giant knotweed (Reynoutria sachalinensis, RS) extract is a known elicitor of plant defenses but its mode of action remains elusive. The aim of this study was to investigate the mechanisms of foliar RS applications and how these affect PM severity and crop performance when used alone or in combination with genetic resistance. RS foliar treatments significantly reduced conidial germination and PM severity on both an intermediate resistance (IR) and a susceptible (S) genotype. RS application triggered plant defense responses, which induced the formation of callose papillae, hydrogen peroxide accumulation and the Salicylic acid (SA) - dependent pathway. Increased SA production was detected along with increased p-coumaric and caffeic acid concentrations. These findings clearly indicate that RS elicits plant defenses notably as a consequence of SA pathway induction.

Volatile profile of Greek dried white figs (Ficus carica L.) and investigation of the role of ß-damascenone in aroma formation in fig liquors.

BACKGROUND: During an investigation of the chemical profile of Greek figs (Ficus carica L.), several aqueous ethanol extracts (liquors) were prepared from dried Smyrna fig varieties cultivated in the two major fig-producing geographical areas in Greece: Peloponnese and Evia Island. The distinctive aroma observed among the prepared fig liquors led to the investigation of the odor profile of the different fig cultivars through HS-SPME coupled with GC/MS analysis, with focus on the factors that affect it before and during the preparation of the respective liquors. RESULTS: Significant variation in volatiles was noticed among all fig cultivars, as also between each fig cultivar pulp and the respective liquor. The observed diversity was a result of chemical reactions taking place in the ethanol matrix during the preparation of the liquor. The 'key' odor compound of dried fig aroma was found to be ß-damascenone. Owing to its low detection threshold and minute quantity in fig cultivars, the presence of ß-damascenone was furthermore confirmed through GC/MS/MS and GC/TOF-MS. ß-Damascenone was identified in variable quantities among fig varieties and their liquors, predominating in Kalamon fig cultivar of Peloponnese region, while its amount was found to be dependent on the postharvest storage time and preservation process of dried figs. CONCLUSION: Each of the studied fig cultivars and liquors showed a unique aroma profile, and the obtained results were used for the preparation of the first dried fig liqueur for potential commercial use with the highest content of ß-damascenone. © 2017 Society of Chemical Industry.

Rapid determination of famoxadone and cymoxanil in commercial pesticide formulation by high performance liquid chromatography using a C18 monolithic rod column.

The extensive use of plant protection products in urban and rural pest control obliges to develop valid analytical methods for their successful and reliable quality control. An analytical procedure for the simultaneous determination of famoxadone and cymoxanil, by reversed phase high performance liquid chromatography based on the use of a monolithic C18 column has been developed and validated. The method involved the extraction of the active ingredients by sonication of the sample with acetonitrile and direct injection on a reversed phase liquid chromatographic system. The repeatability of the method expressed as relative standard deviation (%RSD), was lower than 1 % for both compounds. The limits of quantification for famoxadone and cymoxanil were 10 and 16 µg mL(-1) respectively. The new method involves a considerable reduction in time for both sample preparation and analysis. The proposed analytical procedure is accurate and precise.

Endosulfan in wind-transported African dust depositions in Crete.

The presence of endosulfan in samples of African dust after a typical red dust storm in May 2007 was investigated. The samples were collected from a remote and mountainous area of Crete (Greece) where olive groves are cultivated. Endosulfan I, endosulfan II and endosulfan sulphate were detected at concentrations of 2.7, 1.4 and 1.1 ng/g, respectively, indicating that long range aeolian dust transport could be a possible source of contamination of olive cultivations.

Facile and rapid determination of contamination in sulphur pesticide formulations by liquid chromatography-tandem mass spectrometry.

Up to 7% of pesticide products in the European market are illegal, counterfeit or of poor quality. As a result, regulatory authorities are required to determine a wide variety of impurities in many different pesticide formulations. A simple, rapid and exceptionally reliable LC-MS-MS method for the determination of carbendazim residual quantities in sulphur formulations, used in organic agriculture, has been developed and validated. Linearity of response was established (R (2) = 0.9997) over a wide range of concentrations (0.01-2 microg/mL). Recovery ranged from 94% to 101%. LOD and LOQ were 0.003 microg/mL and 0.005 microg/mL, respectively, and lack of interference was confirmed.

Bee honey as an environmental bioindicator of pesticides' occurrence in six agricultural areas of Greece.

The pollution of six agricultural areas of Greece (north, central, south) by insecticides used in crop protection has been investigated utilizing, as a bioindicator, bee honey produced in those areas. Honey samples collected randomly from apiaries located in those areas were analyzed for pesticide residues with a multianalytical method, able to determine simultaneously up to 10 organophosphorous insecticides from the same honey extract. Findings concerning the acaricide coumaphos were also included, even though it is not used in crop protection. Coumaphos is used to control the mite Varroa destructor, an external parasite of the honeybee. The above areas are cultivated in large extent with citrus trees or cotton or sunflower crops, which are good forages for honeybees. The main pests of those crops are insects; hence, insecticides are used on a large scale for crop protection. The most contaminated samples originated from citrus groves; 16 out of 19 had pesticide residues: 4 samples had chlorfenvinphos (21.05%), 10 had chlorpyrifos (52.63%) and 2 had phorate (10.53%). Out of 17 samples from cotton fields, residues were found in 8, phorate in 6 (35.29%), chlorfenvinphos in 1 (5.88%), and chlorpyrifos in 1 (5.88%). Out of nine samples from fields of sunflower, four had phorate residues (44.44%). In brief, from the 50 analyzed samples, residues of chlorfenvinphos were detected in 5 samples (10%), residues of chlorpyrifos in 11 samples (22%), and residues of phorate in 12 samples (24%). Their levels ranged between 0.70 and 0.89 microg/kg. Coumaphos residues ranged from 0.10 up to 4.80 microg/kg and were derived exclusively from beehives treated with Perizin (the commercial formulation of coumaphos) for Varroa control. This study indicates that in agricultural areas with developed apiculture, useful information about the occurrence and the distribution of pesticide residues due to crop protection treatments can be derived from the analysis of randomly collected honey samples, used as bioindicators. It also shows that, very often, the chemicals used by apiculturists inside the hives in order to control disease are the main pollutants of the produced honey.